CA1107444A - Light-sensitive materials - Google Patents
Light-sensitive materialsInfo
- Publication number
- CA1107444A CA1107444A CA268,315A CA268315A CA1107444A CA 1107444 A CA1107444 A CA 1107444A CA 268315 A CA268315 A CA 268315A CA 1107444 A CA1107444 A CA 1107444A
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- CA
- Canada
- Prior art keywords
- group
- formula
- phenyl
- hydrogen
- represent hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/44—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by —CHO groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/49—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups
- C07C205/56—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups bound to carbon atoms of six-membered aromatic rings and carboxyl groups bound to acyclic carbon atoms of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
- C07C47/24—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/30—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings
- C07C57/42—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings having unsaturation outside the rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
- C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
- C07C59/66—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings
- C07C59/68—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings the oxygen atom of the ether group being bound to a non-condensed six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F20/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polymerisation Methods In General (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
? photopolymerisable material suitable for use in the production of lithographic printing plates comprises a polymer which includes a plurality of structural units represented by the Formula:
in which R1 represents a hydrogen atom or methyl group;
R2 represents hydrogen atom, an alkyl or substituted alkyl group, an aryl or substituted aryl group, or a heterocyclic or substituted heterocyclic group; R3, R4 and R5, which may be the same or different, each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an aralkyl group, an aralkoxy group or an alkoxy carbonyl group; Z represents a hydroxyl group, or an ester group and a is an integer greater than or equal to 1.
The polymer may be produced by reacting a polymer of 2,3-epoxy propyl acrylate or 2,3-epoxy propyl methacrylate with an acid of formula R2-(CR3-CR4)??=C(OOH)2.
? photopolymerisable material suitable for use in the production of lithographic printing plates comprises a polymer which includes a plurality of structural units represented by the Formula:
in which R1 represents a hydrogen atom or methyl group;
R2 represents hydrogen atom, an alkyl or substituted alkyl group, an aryl or substituted aryl group, or a heterocyclic or substituted heterocyclic group; R3, R4 and R5, which may be the same or different, each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an aralkyl group, an aralkoxy group or an alkoxy carbonyl group; Z represents a hydroxyl group, or an ester group and a is an integer greater than or equal to 1.
The polymer may be produced by reacting a polymer of 2,3-epoxy propyl acrylate or 2,3-epoxy propyl methacrylate with an acid of formula R2-(CR3-CR4)??=C(OOH)2.
Description
~7~4 ~his invention relates to photopolymeri6able materials.
Numerous light-sensitive compositions are known which are based on solvent soluble light-sensitive polymers, such as poly(vinyl cinnamate).
'iuch a composi.tion for instance when applied in the form of a thin layer to a suitable substrate to form a printing plate or a resist has the disadvantag~e thatafter the hardening reaction has occurred under the influence of actinic radiation~
an expensive and pos~ibly toxic and/or inflammable solvent is required to remove the unhardened areas.
It is an obje~t of the present invention to provide a photopolymer;Sable material. which, in its un hardened form~
is soluble in an aqueous solution of inorganic sal~s.
. Accordin~ to one aspect of the present invention, there is provided a photopolymerisable material.., which~comprises a polymer including a plurality of structural uni.ts represented.
.. by the Formula (I);
,. , R1 . : I
,. - C-- C~I2 .,,, C = O
, O
. C~2 ''' I
CII - Z ~5 lI2- O- ,C,-,C _ C ~ (CR4=CR~)a - R2 in which R1 represents a hydrogen atom or a methyl group:~
: R2 represents a hydrogen atom~ an alkyl or substituted alkyl .
-.
Numerous light-sensitive compositions are known which are based on solvent soluble light-sensitive polymers, such as poly(vinyl cinnamate).
'iuch a composi.tion for instance when applied in the form of a thin layer to a suitable substrate to form a printing plate or a resist has the disadvantag~e thatafter the hardening reaction has occurred under the influence of actinic radiation~
an expensive and pos~ibly toxic and/or inflammable solvent is required to remove the unhardened areas.
It is an obje~t of the present invention to provide a photopolymer;Sable material. which, in its un hardened form~
is soluble in an aqueous solution of inorganic sal~s.
. Accordin~ to one aspect of the present invention, there is provided a photopolymerisable material.., which~comprises a polymer including a plurality of structural uni.ts represented.
.. by the Formula (I);
,. , R1 . : I
,. - C-- C~I2 .,,, C = O
, O
. C~2 ''' I
CII - Z ~5 lI2- O- ,C,-,C _ C ~ (CR4=CR~)a - R2 in which R1 represents a hydrogen atom or a methyl group:~
: R2 represents a hydrogen atom~ an alkyl or substituted alkyl .
-.
-2-744~
./
group, an aryl or substituted aryl group, or a heterocyclic . or substituted heterocyclic group, R3, R4 and R5, which may be the same or different, each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an aralkyl group, an aralkoxy group or an alkoxy carbonyl group; Z represents a hydroxyl group or an ester group; and a lS an integer greater than or equal to 1.
. According to a preferred feature of the invention, the polymer also includes a plurality of structural units having : the Formula (II):
~Rl - C - CHz-C O
l CH _ zl R
I
CHz - O - C - C = C - (CR4 = CR9)b - R2 .. O R6 20 in which Zl represents a hydroxyl group, an ester group or a halogen atom; R~ to R5 represent the same as in formula I;
R6 represents the same as R3 to R5 in Formula I; and in which b is either O or an integer greater than or equal to 1.
According to a further preferred feature the polymer also includes a plurality of structural units havina the Formula bm:~D
' , ~ '' ' ' . . .
( I I I ) :
R
l --O
fH 2 . CH_ Zl : CH2--O--C--R' . 11 in which Rl represents the same as in formulae I and II; R' represents an alkyl or substituted alkyl group, an aryl or .; substituted aryl group, or a heterocyclic or substituted heterocyclic group, and Zl represents a hydroxyl group, an ester group or a halogen atom.
. According to a further preferred feature, the polymer also includes structural units derived from at least one other unsaturated addition polymerisable monomer.
In the ~ormulae I and II, R2 may be, for example phenyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, . 20 2-aminophenyl, 3-aminophenyl, 4-aminophenyl, 2-azidophenyl, 3-azidophenyl, 4-azidophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-chlorophenyl, 3-chlorophenyl~ 4-chlorophenyl, 4-phenylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl,
./
group, an aryl or substituted aryl group, or a heterocyclic . or substituted heterocyclic group, R3, R4 and R5, which may be the same or different, each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an aralkyl group, an aralkoxy group or an alkoxy carbonyl group; Z represents a hydroxyl group or an ester group; and a lS an integer greater than or equal to 1.
. According to a preferred feature of the invention, the polymer also includes a plurality of structural units having : the Formula (II):
~Rl - C - CHz-C O
l CH _ zl R
I
CHz - O - C - C = C - (CR4 = CR9)b - R2 .. O R6 20 in which Zl represents a hydroxyl group, an ester group or a halogen atom; R~ to R5 represent the same as in formula I;
R6 represents the same as R3 to R5 in Formula I; and in which b is either O or an integer greater than or equal to 1.
According to a further preferred feature the polymer also includes a plurality of structural units havina the Formula bm:~D
' , ~ '' ' ' . . .
( I I I ) :
R
l --O
fH 2 . CH_ Zl : CH2--O--C--R' . 11 in which Rl represents the same as in formulae I and II; R' represents an alkyl or substituted alkyl group, an aryl or .; substituted aryl group, or a heterocyclic or substituted heterocyclic group, and Zl represents a hydroxyl group, an ester group or a halogen atom.
. According to a further preferred feature, the polymer also includes structural units derived from at least one other unsaturated addition polymerisable monomer.
In the ~ormulae I and II, R2 may be, for example phenyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, . 20 2-aminophenyl, 3-aminophenyl, 4-aminophenyl, 2-azidophenyl, 3-azidophenyl, 4-azidophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-chlorophenyl, 3-chlorophenyl~ 4-chlorophenyl, 4-phenylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl,
3,4-methylenedioxyphenyl, 2-methylphenyl, 3-methylphenyl,
4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, : 4-i~opropylphenyl, 3, ~-di.chlorophenyl, 2,4-dichlor.ophenyl, 2,4-di~itrophenyl, : .
bm~
:
2-nitro-5-chlorophenyl, 2-3-dimethoxyphenyl; 3,4-dimethoxy-phenyl, 2,4-dimethoxyphenyl, 2,5-dimethoxyphenyl, 3,5-dimethoxyphenyl, 2-ethoxyphenyl, 3,4-diethoxyphenyl, 4-dimethylaminophenyl, 4-diethylaminophenyl, l-naphthyl, 2-naphthyl, 2-ethoxy-1-naphthyl, 2-methoxy-1-naphthyl, 4,8-; dimethoxy-l-naphthyl, 2,7-dimethoxy-1-naphthyl, 1-4-dimethoxy-2-naphthyl, 6-methoxy-2-naphthyl, 4-chloro-1-naphthyl, 2-chloro-1-naphthyl, 4-bromo-1-naphthyl, 5-bromo-l-naphthyl, l-bromo-2-naphthyl, 5-bromo-2-naphthyl, 4-nitro-l-naphthyl, 1-nitro-2-naphthyl, 9-anthranyl, 10-methyl-9-anthranyl, 2-furyl, 5-methyl-2-furyl, 5-bromo-2-furyl, 5-chloro 2-furyl, 5-iodo-2-furyl, 5-nitro-2-furyl, 2-thienyl, 5-bromo-2-thienyl, 3,4-dichloro-2-thienyl, 5-nitro-2-thienyl, l-methyl-2-pyrrolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 6-methyl-2-pyridyl~ 4-maleimidophenyl or 4-acetamido phenyl.
Particularly preferred embodiments are: the polymers where, in formula I, RZ represents phenyl and R3, R4 and R' represent hydrogen; R2 represents 2-nitrophenyl and R3, R4and R5 hydrogen; R2 represents 3-nitrophenyl and R3, R4 and R3 represent hydrogen; R2 represents phenyl, R9 represents chloro and R4 and R5 represent hydrogen; and R2 represents 4-nitrophenyl, R9 represents chloro and R4 and R~ represent hydrogen; the polymers where, i~ for~ula IIr and particularly when-b = O~ R2 R5 and R all represent hydrogen; R2 and R3 represent hydrogen and R6 repxesents m~thyl; R2 represents phenyl and R5 ~nd ~-~epresent hydrogeni R2 represents 4-metho~yphenyl f R2 represents hydrogen ,
bm~
:
2-nitro-5-chlorophenyl, 2-3-dimethoxyphenyl; 3,4-dimethoxy-phenyl, 2,4-dimethoxyphenyl, 2,5-dimethoxyphenyl, 3,5-dimethoxyphenyl, 2-ethoxyphenyl, 3,4-diethoxyphenyl, 4-dimethylaminophenyl, 4-diethylaminophenyl, l-naphthyl, 2-naphthyl, 2-ethoxy-1-naphthyl, 2-methoxy-1-naphthyl, 4,8-; dimethoxy-l-naphthyl, 2,7-dimethoxy-1-naphthyl, 1-4-dimethoxy-2-naphthyl, 6-methoxy-2-naphthyl, 4-chloro-1-naphthyl, 2-chloro-1-naphthyl, 4-bromo-1-naphthyl, 5-bromo-l-naphthyl, l-bromo-2-naphthyl, 5-bromo-2-naphthyl, 4-nitro-l-naphthyl, 1-nitro-2-naphthyl, 9-anthranyl, 10-methyl-9-anthranyl, 2-furyl, 5-methyl-2-furyl, 5-bromo-2-furyl, 5-chloro 2-furyl, 5-iodo-2-furyl, 5-nitro-2-furyl, 2-thienyl, 5-bromo-2-thienyl, 3,4-dichloro-2-thienyl, 5-nitro-2-thienyl, l-methyl-2-pyrrolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 6-methyl-2-pyridyl~ 4-maleimidophenyl or 4-acetamido phenyl.
Particularly preferred embodiments are: the polymers where, in formula I, RZ represents phenyl and R3, R4 and R' represent hydrogen; R2 represents 2-nitrophenyl and R3, R4and R5 hydrogen; R2 represents 3-nitrophenyl and R3, R4 and R3 represent hydrogen; R2 represents phenyl, R9 represents chloro and R4 and R5 represent hydrogen; and R2 represents 4-nitrophenyl, R9 represents chloro and R4 and R~ represent hydrogen; the polymers where, i~ for~ula IIr and particularly when-b = O~ R2 R5 and R all represent hydrogen; R2 and R3 represent hydrogen and R6 repxesents m~thyl; R2 represents phenyl and R5 ~nd ~-~epresent hydrogeni R2 represents 4-metho~yphenyl f R2 represents hydrogen ,
-5-bm~
.
and R6 represents cyano; R2 represents 4-chloro-phenyl, R5 represents hydrogen and R6 represents phenyl; R2 represents 4-methyl phenyl, R5 is hydrogen and R6 is phenoxy; R2 represents 4-azido phenyl, R5 represents hydro~en and R6 represents cyano;
and R represents 2-furyl, and R5 and R6 represent hydrogen;
the polymers where, in formula II when b = 1, R2 represents phenyl, R3, R4 and R5 represent hydrogen and R6 is cyano;
R2 is phenyl, R3, R4 and R5 represent hydrogen and R6 represents ethoxy carbonyl; and R2 represents phenyl, R3 and R4 represent~
hydrogen, R5 represents methyl and R6 represents cyano: the polymers where, in formula III, R7 represents methyl and z1 represents hydroxyl; R7 represents heptyl and Z represents hydroxyl; R7 represents ethyl and Z represents chlorine; R7 represents tr~chloromethyl and ~ represents hydroxyl.
In thecase where the polymer also includes structural units derived from ano-ther unsaturated addition polymerisable monomer, the monomer may be acrylic or methacrylic acid; an acrylâte or methacrylate; a hydroxy acrylate or methacrylate;
acrylamide or a substituted acrylamide; methacrylamide or a substituted methacrylamide; acrylonitrile; methacrylonitrile;
vinyl chloride; vinyl acetate; styrene or a substituted styrene such as c~-methyl styrene, 4-chlo~ostyrene or p-methoxy styrene;
a vinyl ether such as isobutylvinyl ether, 2-chlorovinyl ether, or phenyl vinyl ether; an aliphatic diene, such as chloroprene, butadiene or hexadiene. The presence of such structural units can confer certain desirable advantages~ such as better ink receptivity, better ~brasion resistance during printing : .
~ -6-:"
~7444 and/or better sensitivity to light.
The polymer in the material of the present invention may be produced by reacting a polymer of 2,3-epoxypropyl acrylate or of 2,3-epoxypropyl methacrylate (elther a homopolymer or a copolymer of 2,3-epoxypropyl acrylate or methacrylate with~for example, one of the foregoing monomers) with an ethylenically unsaturated dicarboxylic acid of formula /COOH
R2 _ (CR3 = CR4) - G =C
wherein a and R2 to R5 have the above specified meanings.
The radiation sensitivity of the polymer in the material of ~he present invention is provided by the double gonds and its alk~li solubility i5 provided by the unreacted carboxyl groups.
Under suitable conditions, however, the above reaction can be arranged so that not all the epoxy grou~s of the polymer of 2,3-apoxypropyl acrylate or methacrylate react with the di-carboxylic acid. It is then possible to react thes(? unreacted units with an ethylenically unsaturated monocarboxylic acid (or halide thereof) of formula ~R6 R2 _ (CR~ - CR4)b - C = C
wherein b and R2 to R6 have the above specified meanings to produce structural units of ~ormula II and/or with a saturate-l carboxylic acid (or a halide th~-reof) of for~ula ..
:
.
;~ "` 11al7444 R7 - COOH wherein R7 has the meaning specified above to produce structural units of Formula III. The structural units of Formula II give increased radiation sensitivity without alkali solubility and the structural units of Formula III give increased ~- ink receptivity.
. The reaction of the epoxy groups with the acids and acid halides produce structural units containing secondary hydroxyl groups or halogen atoms (represented by Z and Zl in Formulae I, II and III). In the case where secondary hydroxyl groups are produced, these may advantageously be reacted with a carboxylic acid or ester forming derivative thereof such as ,. i ;. the acid halide or anhydride whereby the secondary hydroxyl groups are converted into ester groups. By reacting the secondary hydroxyl groups with the acids used to produce the structural ., units of Formula II, (or with ester forming de-rivatives of such -~ acids) increased radiation sensitivity is obtained whereas the : . use of the acids used to produce the structural units of : Formula III (or ester forming derivatives of .such acids) will give increased ink receptivity.
. Thus, by varying the reactants, and the reaction conditions, it i~ possible to produce photopolymerisable materials having varying properties in respect of alkali solubility, radiation sensitivity, ink receptivity and abrasion resistance.
. Dyes, pigments, leuco dyes, plasticisers and/or sensitisers may be included in the photopolymerisable material which may .
: ~ -8-: ~ , r bm: ~ 1'.4.~, . , ` .
4~
be coated on to a suitable substrate of, for example~
aluminium, to form a radiation sensitive plate for subsequent exposure.
~he fbllowing Examples illustrate the inventio~, Certain of the polymers and carboxylic acids used in the Examples were prepared as described in the following syntheses:-. .
~37~
S~nthesis Al Pol~ (2.~_epox~propxl methacr~late~ ~9 d'-Azodiisobutyro-nitrile (8g) was mixed with 2,3-epo~propylmethacrylate (200g) and slowly added to 2_b~tanone (400 ml~ under a nitrogen at~osphere at 7 C. ~his temperature was maintained for 3 hrs. and then increased to 80C for 2 hrs. The cooled solution was diluted with 2_butanone (1400 ml), poured into 40-60 petroleum ether (12 1) and the product collected and dried to yield 195 g. of poly_ (2,3-epoxypropyl methacrylate) having an epoxide equivalent of 158.7.
Pol~ (2L3-epox~pro~l acrYlate) a, a'-Azodiisobutyronitrile (0.36 g) was mixed with 2,3_epox~propyl acrylate (18.0g) and the solution slowly added to a mixture of 2-butanone (60 mQ) and ethanol 20 mQ ) under a nitrogen atmosphere at 60C. This temperature was maintained for one hour, raised to 70C
for two hours and then to 80C for a further two hours. The cooled solution was diluted with 2_butanone (100 m~); poured into 40-60 petroleum ether (1~) and the product collected and dried to yield 17.2 g of poly_(2,3-epoxypropylacrylate) having an epoxide equivalent of 132.30.
S~nthesis A3 Poly(2~3_epoxY~rop~1 methacr~late-co dodec~l methacrylate~.
A mixture of 2,3-epoxypropylmethacrylate (16.63 g),dodecyl methacrylate (3.31g), dodecyl thiol (0~4g) and a,a'-azo-.. ..
diisobuty~nitrile (0.8g) was polymerised in 2-butanone (50 mQ) by the method described in Synthesis Al to yield~l5 2 g of the required co-polymer9 having an epoxide equivalent of 178.2.
. .
~`
,` -'1 0_ S~nthesis A4 Poly (2,3-epoxypro~ylmethacrylate-co-styrene). A mixture of 2,3_epoxypropyl methacrylate (18.49g), styrene (1.51g), dodecyl thiol (0.8g) and a,a'azodiisobutyronitrile (lg) was polymerised in 2-buta~one (50 mR) by the method described in Synthesis Al to ~ield 18.4g of the required copolymer havlng an epoxide equivaleDt of 171.
Synthesis A5 Poly(2,~ epoxypro~lacrylate-co-acryloni~$1e).
A mixture of 2,3_epoxypropylacrylate (20g~, ac~ylonitrile (0.92g)~ dodecyl th~l (0.4g) and ~,a'-azodiisobutyronitrile (O.8g) was polymerised in a mixture of 2-butanone (50 mQ) and ethanol(20 m~) by the method described in Synthesis A2 to yield 20.lg of the required copolymer havin~ an epoxide equivalent'of 145.
S~nthesis Bl (i) 3-nitro cinnam~dehyde was prepared by Claisen-Schmidt condensation of 3-nitrobenzaldehyde with acetaldehyde as follows.
. . .
A solution of 3_nitrobenzaldehyde (80g 0.53 mol.) in A
e~anol (1.6Q) was treated with water (1.8R).Acetaldehyde (36 mQ., 0.644 mol.) was added followed by a 10% aqueous solution o~ sodium h~droxide r56 m~) and the mixture stirred for 5 hrs at 20C. The mixture was decanted and the residue ~oiled with 25% acetic acid (2~), cooled and the crude product (13.7g) collected and us~d without f~rther purificati~n as follows.
~ ii) 3-nitro cinnamylidene malonic acid was prepared by reacting 3~nitro cinnamaldehyde (13.7g) with malonic acid (8.05g 0.077 mol.) in glacial acetic acid (20 ml) at 100C for _11 -. ' ' ';, ~
.
and R6 represents cyano; R2 represents 4-chloro-phenyl, R5 represents hydrogen and R6 represents phenyl; R2 represents 4-methyl phenyl, R5 is hydrogen and R6 is phenoxy; R2 represents 4-azido phenyl, R5 represents hydro~en and R6 represents cyano;
and R represents 2-furyl, and R5 and R6 represent hydrogen;
the polymers where, in formula II when b = 1, R2 represents phenyl, R3, R4 and R5 represent hydrogen and R6 is cyano;
R2 is phenyl, R3, R4 and R5 represent hydrogen and R6 represents ethoxy carbonyl; and R2 represents phenyl, R3 and R4 represent~
hydrogen, R5 represents methyl and R6 represents cyano: the polymers where, in formula III, R7 represents methyl and z1 represents hydroxyl; R7 represents heptyl and Z represents hydroxyl; R7 represents ethyl and Z represents chlorine; R7 represents tr~chloromethyl and ~ represents hydroxyl.
In thecase where the polymer also includes structural units derived from ano-ther unsaturated addition polymerisable monomer, the monomer may be acrylic or methacrylic acid; an acrylâte or methacrylate; a hydroxy acrylate or methacrylate;
acrylamide or a substituted acrylamide; methacrylamide or a substituted methacrylamide; acrylonitrile; methacrylonitrile;
vinyl chloride; vinyl acetate; styrene or a substituted styrene such as c~-methyl styrene, 4-chlo~ostyrene or p-methoxy styrene;
a vinyl ether such as isobutylvinyl ether, 2-chlorovinyl ether, or phenyl vinyl ether; an aliphatic diene, such as chloroprene, butadiene or hexadiene. The presence of such structural units can confer certain desirable advantages~ such as better ink receptivity, better ~brasion resistance during printing : .
~ -6-:"
~7444 and/or better sensitivity to light.
The polymer in the material of the present invention may be produced by reacting a polymer of 2,3-epoxypropyl acrylate or of 2,3-epoxypropyl methacrylate (elther a homopolymer or a copolymer of 2,3-epoxypropyl acrylate or methacrylate with~for example, one of the foregoing monomers) with an ethylenically unsaturated dicarboxylic acid of formula /COOH
R2 _ (CR3 = CR4) - G =C
wherein a and R2 to R5 have the above specified meanings.
The radiation sensitivity of the polymer in the material of ~he present invention is provided by the double gonds and its alk~li solubility i5 provided by the unreacted carboxyl groups.
Under suitable conditions, however, the above reaction can be arranged so that not all the epoxy grou~s of the polymer of 2,3-apoxypropyl acrylate or methacrylate react with the di-carboxylic acid. It is then possible to react thes(? unreacted units with an ethylenically unsaturated monocarboxylic acid (or halide thereof) of formula ~R6 R2 _ (CR~ - CR4)b - C = C
wherein b and R2 to R6 have the above specified meanings to produce structural units of ~ormula II and/or with a saturate-l carboxylic acid (or a halide th~-reof) of for~ula ..
:
.
;~ "` 11al7444 R7 - COOH wherein R7 has the meaning specified above to produce structural units of Formula III. The structural units of Formula II give increased radiation sensitivity without alkali solubility and the structural units of Formula III give increased ~- ink receptivity.
. The reaction of the epoxy groups with the acids and acid halides produce structural units containing secondary hydroxyl groups or halogen atoms (represented by Z and Zl in Formulae I, II and III). In the case where secondary hydroxyl groups are produced, these may advantageously be reacted with a carboxylic acid or ester forming derivative thereof such as ,. i ;. the acid halide or anhydride whereby the secondary hydroxyl groups are converted into ester groups. By reacting the secondary hydroxyl groups with the acids used to produce the structural ., units of Formula II, (or with ester forming de-rivatives of such -~ acids) increased radiation sensitivity is obtained whereas the : . use of the acids used to produce the structural units of : Formula III (or ester forming derivatives of .such acids) will give increased ink receptivity.
. Thus, by varying the reactants, and the reaction conditions, it i~ possible to produce photopolymerisable materials having varying properties in respect of alkali solubility, radiation sensitivity, ink receptivity and abrasion resistance.
. Dyes, pigments, leuco dyes, plasticisers and/or sensitisers may be included in the photopolymerisable material which may .
: ~ -8-: ~ , r bm: ~ 1'.4.~, . , ` .
4~
be coated on to a suitable substrate of, for example~
aluminium, to form a radiation sensitive plate for subsequent exposure.
~he fbllowing Examples illustrate the inventio~, Certain of the polymers and carboxylic acids used in the Examples were prepared as described in the following syntheses:-. .
~37~
S~nthesis Al Pol~ (2.~_epox~propxl methacr~late~ ~9 d'-Azodiisobutyro-nitrile (8g) was mixed with 2,3-epo~propylmethacrylate (200g) and slowly added to 2_b~tanone (400 ml~ under a nitrogen at~osphere at 7 C. ~his temperature was maintained for 3 hrs. and then increased to 80C for 2 hrs. The cooled solution was diluted with 2_butanone (1400 ml), poured into 40-60 petroleum ether (12 1) and the product collected and dried to yield 195 g. of poly_ (2,3-epoxypropyl methacrylate) having an epoxide equivalent of 158.7.
Pol~ (2L3-epox~pro~l acrYlate) a, a'-Azodiisobutyronitrile (0.36 g) was mixed with 2,3_epox~propyl acrylate (18.0g) and the solution slowly added to a mixture of 2-butanone (60 mQ) and ethanol 20 mQ ) under a nitrogen atmosphere at 60C. This temperature was maintained for one hour, raised to 70C
for two hours and then to 80C for a further two hours. The cooled solution was diluted with 2_butanone (100 m~); poured into 40-60 petroleum ether (1~) and the product collected and dried to yield 17.2 g of poly_(2,3-epoxypropylacrylate) having an epoxide equivalent of 132.30.
S~nthesis A3 Poly(2~3_epoxY~rop~1 methacr~late-co dodec~l methacrylate~.
A mixture of 2,3-epoxypropylmethacrylate (16.63 g),dodecyl methacrylate (3.31g), dodecyl thiol (0~4g) and a,a'-azo-.. ..
diisobuty~nitrile (0.8g) was polymerised in 2-butanone (50 mQ) by the method described in Synthesis Al to yield~l5 2 g of the required co-polymer9 having an epoxide equivalent of 178.2.
. .
~`
,` -'1 0_ S~nthesis A4 Poly (2,3-epoxypro~ylmethacrylate-co-styrene). A mixture of 2,3_epoxypropyl methacrylate (18.49g), styrene (1.51g), dodecyl thiol (0.8g) and a,a'azodiisobutyronitrile (lg) was polymerised in 2-buta~one (50 mR) by the method described in Synthesis Al to ~ield 18.4g of the required copolymer havlng an epoxide equivaleDt of 171.
Synthesis A5 Poly(2,~ epoxypro~lacrylate-co-acryloni~$1e).
A mixture of 2,3_epoxypropylacrylate (20g~, ac~ylonitrile (0.92g)~ dodecyl th~l (0.4g) and ~,a'-azodiisobutyronitrile (O.8g) was polymerised in a mixture of 2-butanone (50 mQ) and ethanol(20 m~) by the method described in Synthesis A2 to yield 20.lg of the required copolymer havin~ an epoxide equivalent'of 145.
S~nthesis Bl (i) 3-nitro cinnam~dehyde was prepared by Claisen-Schmidt condensation of 3-nitrobenzaldehyde with acetaldehyde as follows.
. . .
A solution of 3_nitrobenzaldehyde (80g 0.53 mol.) in A
e~anol (1.6Q) was treated with water (1.8R).Acetaldehyde (36 mQ., 0.644 mol.) was added followed by a 10% aqueous solution o~ sodium h~droxide r56 m~) and the mixture stirred for 5 hrs at 20C. The mixture was decanted and the residue ~oiled with 25% acetic acid (2~), cooled and the crude product (13.7g) collected and us~d without f~rther purificati~n as follows.
~ ii) 3-nitro cinnamylidene malonic acid was prepared by reacting 3~nitro cinnamaldehyde (13.7g) with malonic acid (8.05g 0.077 mol.) in glacial acetic acid (20 ml) at 100C for _11 -. ' ' ';, ~
6 hrs. After cooling, the product was collected,washed and dried to yield 8.9g. of the desired product m.p 185-187C.
. .
Synthesis B2 Cinnamylidene malonic acid was prepared by reacting cinnamaldeh~de (125g 0.95 mol) with malonic acid (104 g, 1 mol) in glacial acetic acid (200 mQ) according to the method described in Synthesis Bl(ii) m p 206-208C.
Synthesis B~
2_nitrocinnamylidene mal~nic acid was prepared by reacting 2-nitro cinnamaldehyde (lOOg 0.614 mol) with malonic acid (lOOg 0.96 mol.) in glacial acetic acid (95 mQ) according to the method described in Synthesis Bl m.p 185_187C.
Synthesis B4 (i) B-chlorocinnamaldehyde was prepared by the following method. Fhosphoryl chloride (24 mQ, 0.26 mol.) was slowly added to anhy~rous dimethyl formamide (40 ml) mai~taining a temperature of 0C and the resulting solution stirred for 30 minutes. Acetophenone (24 g 0 2 mol.) was also dissolved in anhydrous dimethyl formamide (25 mQ) and the mixture slowly added to the phosphoryl chloride solution Whilst stirring, the reaction mixture was allowed to attain room temperature, stirred for two hours and then poured into an agitated solution of sodium acetate (300 g) in water (750 mQ), After stirring for 30 minutes the product was extracted into ether, the ether ext~acts were dried over magnesium sulphate and the ether was then re~oved to yield _12-74~4 28.8g of crude product which was used without further purification as follows.
- (ii) ~-chlorocinnamylidene malonic ac~d was prepared by reacting ~-chlorocinnamaldehyde (16,65g) with malonic acid (10.4g) 0,1 mol) in glacial acetic acid ~lOmQ) according to the method described in Synthesis Bl (ii~ to yield 7.5g of the desired product m,p,158-160C (dec,) S~nthesis B5 ~i) 4-nitro-~-chlorocinnamaldehyde was prepared by a modification of the procedure described in Synthesis B4(i) ' to yield the desired compound which was recrystallised from ethanol, m~p. 72-74C, (ii) 4-nitro-~-chlorocinnamylidene malonic acid was prepared by reacting 4-nitro-~-chlorocinnamaldehyde (80g 0,39.
mol,) with maloniG acid (41g " 0.4 mol). in glacial acetic acid (50 mQ) at 100C for 6 hours, The cooled solution was poured into a 10% aqueous solution of sodium hydroxide (300 mQ), extracted with ether and the aqueous layer acidified with 30 aqueous hydrochloric acid ~300 mQ) to yield 10.45g of the desired compound m.p, 173-175C.
.~. .
Synthesis Cl.
Cinnamylidene-~-cyanoacetic acid was prepared by reacting cinnamaldehyde (252 mQ 2,0 mol,) with azeotropically dried cyanoacetic acid (170 g., 2,0 mol.) in glacial acetic acid (50 mQ) at 100C for 2 hrs. Toluene (130 mQ) was then added and water removed by azeotropic distillation for a period of 5 hrs, The toluene was distilled off, the reaction mixture cooled and the crystalline product collected, washed with cold glacial acetic acid followed by hot water to yield 235 g, :, .
bm~ '' t ' ~
:
,. ~.
~ 7`~44 . ., ~ .
of the desired product m.p. 210-212C.
~ynethesis C2 4-chloro~ henyl cinnamic acid was prepared by reacting 4-chlorobenzal~dehyde (35g. ~ 0.25 mol.) with phenylacetic acid (37.4g 0.275 mol.) in glacial acetic acid (20 m~) at 100C
for 6 hours. After cooling, the product was collected, washed and dried to yield 31.0g o~ the desired compound, m.p. 204-206C.
S~nthe is C3 4_methyl- ~ ~henoxy cinnamic acid was prepared by reacting 4_methyl benzaldehyde (120g., 1 mol) with phenoxyacetic acid (167g., 1.1 mol) in a mixture of acetic anhydride (250 m~
2~5 mol) and trieth~lamine (101 mQ 1 mol) at 140C for 5 hours. The cooled deep red solution was poured into 5 litres of a mixture of 1 volum~.of concentrated hydrochloric :
acid and 4 volumes of water and the resultant oil separated, washed with water and then with a 20% (w/v) solution of potassium bisulphite (1 litre) to yield the crude product : which was collected, washed and recrystalli~ed from aqueous ~ ethanol to give 22g of the desired compound m.p 188_190C.
i, Synthesis C4 4-az~do_~ cyano cinnamic acid.~was prepared according to the method describçd in Example 3 of British Specification r~ ? ~ ~o~ o~
No.1,377,747. m.p lG0-lG~ dec.
Synthesis C5 Eth~l h~o~en cinnamylidene malonate was prepared by reacting cinnamaldehyde (31.6 mQ0.2633 mol.) with ethyl _14-744~
potassium malona-te (35.7g 0.26 mol) in glacial acetic acid (5.5 m~ ) at 100C for six hours. After cooling~ the product was collected, washed with a little cold acetic acid and then dissolved in water, extracted with ether and the aqueous layer acidified with dilutchydrochloric acid to yield 25.3 g of the desired product.
Synthesis C6 ~ _(2-furyl) acrylic acid was prepared according to the method described in Organic Syntheses, Collective Vol. III Page ; 425, 1955, m.p. 140-141C.
Synthesis C7 a-cyano-~-methylcinnamvlideneacetic acid was prepared by reacting benzyli-lene acetone (49g 0.33mol.) with ethyl cyanoacetate (38g. 0.33 mol) using, as catalyst, a mixture of ammonium acetate (5g) and acetic acid (15g) in benzene (250 m ~ he reaction mixture was refluxed and the water of reaction removed by azeotropic ~1istillation for a period of i five hours. ~he cooled solution was washed with water, dried over magne~ium sulphate and -the solvent evaporated off to yield a yellow crystalline mass.
A solution of potassium hydroxide (7~0g) in methanol (350 m~)was added and the ~ixture refluxed for 6 hour~
cooled, poured into 30/~ hydrochloric acid (400 mQ) and the precipitate collected and recrys-tallised from aqueous ethanol to yield 12.34g of the desired product m~p. 116 _ 118C.
EX~MP~E 1 (i) Prep_aration of a photosensitive 2 alkali soluble resin 5g (0.032 mol) of the polymer prepared in synthesis Al was dissolved in 2-~utanone (100 mR) admixed with cinnamylidene ~ 7~1~4 ':
malonic acid (synthesis B2) (9.17g 0.042 mol) and benzyltri-ethylammonium chloride (0.4g). The mixture was heated at 80C for fi~e hours and then cooled and precipitated into water (2 l). The resultant pale yellow light sensitive polymer was filtered off and driad at 40C in air to yield 10:4g.
The acid equivalent was 492.
(ii) PreParation of a printin~r plate 2g of the light-sensitive polymer was dissolved in 2_butanone (lO0 mR) coated, by means of a horizontal whirler, on to a ., .
sheet of grained and anodised alumiinium and dried by heating at 80C for 2 minutes. Exposure of the resultant light sensitive plate to a 4000 watt pulsed xenon lamp through a negative for 2 minutes followed by immersion in a 5.~/o aqueou~
solution of sodium metasilicate resulted in a printing plate from which many satisfactory copies could be taken.
~i) Preparation of a photosensitive, alkali soluble resin_ 5~ (0.032 mol) of the polymer prepared in Synthesis Al was dissolved in 2_butanone (lO0 m~) and treated with 3_nitrocinnamylidenem~lonic acid (Synthesis Bl) (10.78g 0.41 mol) and benzyltriethylammoni~m chloride (0.4g) and the mixture heated at 80C for four hours. Cinnamylidene-a -cyanoacetic acid (Synthesis Cl) (25.47g 0.128 mol) and benzyltriethylammonium chloride (0.4g) were then added and heating conti~ued a further two hours. The cooled reaction mixture was diluted with an equal volume of 2~butanone, filtered and the filtrates poured into l~ trichloroethane (lL) whereupon a polymer separated as a flocculent yellow precipitate which was collected on a filter, sucked dry
. .
Synthesis B2 Cinnamylidene malonic acid was prepared by reacting cinnamaldeh~de (125g 0.95 mol) with malonic acid (104 g, 1 mol) in glacial acetic acid (200 mQ) according to the method described in Synthesis Bl(ii) m p 206-208C.
Synthesis B~
2_nitrocinnamylidene mal~nic acid was prepared by reacting 2-nitro cinnamaldehyde (lOOg 0.614 mol) with malonic acid (lOOg 0.96 mol.) in glacial acetic acid (95 mQ) according to the method described in Synthesis Bl m.p 185_187C.
Synthesis B4 (i) B-chlorocinnamaldehyde was prepared by the following method. Fhosphoryl chloride (24 mQ, 0.26 mol.) was slowly added to anhy~rous dimethyl formamide (40 ml) mai~taining a temperature of 0C and the resulting solution stirred for 30 minutes. Acetophenone (24 g 0 2 mol.) was also dissolved in anhydrous dimethyl formamide (25 mQ) and the mixture slowly added to the phosphoryl chloride solution Whilst stirring, the reaction mixture was allowed to attain room temperature, stirred for two hours and then poured into an agitated solution of sodium acetate (300 g) in water (750 mQ), After stirring for 30 minutes the product was extracted into ether, the ether ext~acts were dried over magnesium sulphate and the ether was then re~oved to yield _12-74~4 28.8g of crude product which was used without further purification as follows.
- (ii) ~-chlorocinnamylidene malonic ac~d was prepared by reacting ~-chlorocinnamaldehyde (16,65g) with malonic acid (10.4g) 0,1 mol) in glacial acetic acid ~lOmQ) according to the method described in Synthesis Bl (ii~ to yield 7.5g of the desired product m,p,158-160C (dec,) S~nthesis B5 ~i) 4-nitro-~-chlorocinnamaldehyde was prepared by a modification of the procedure described in Synthesis B4(i) ' to yield the desired compound which was recrystallised from ethanol, m~p. 72-74C, (ii) 4-nitro-~-chlorocinnamylidene malonic acid was prepared by reacting 4-nitro-~-chlorocinnamaldehyde (80g 0,39.
mol,) with maloniG acid (41g " 0.4 mol). in glacial acetic acid (50 mQ) at 100C for 6 hours, The cooled solution was poured into a 10% aqueous solution of sodium hydroxide (300 mQ), extracted with ether and the aqueous layer acidified with 30 aqueous hydrochloric acid ~300 mQ) to yield 10.45g of the desired compound m.p, 173-175C.
.~. .
Synthesis Cl.
Cinnamylidene-~-cyanoacetic acid was prepared by reacting cinnamaldehyde (252 mQ 2,0 mol,) with azeotropically dried cyanoacetic acid (170 g., 2,0 mol.) in glacial acetic acid (50 mQ) at 100C for 2 hrs. Toluene (130 mQ) was then added and water removed by azeotropic distillation for a period of 5 hrs, The toluene was distilled off, the reaction mixture cooled and the crystalline product collected, washed with cold glacial acetic acid followed by hot water to yield 235 g, :, .
bm~ '' t ' ~
:
,. ~.
~ 7`~44 . ., ~ .
of the desired product m.p. 210-212C.
~ynethesis C2 4-chloro~ henyl cinnamic acid was prepared by reacting 4-chlorobenzal~dehyde (35g. ~ 0.25 mol.) with phenylacetic acid (37.4g 0.275 mol.) in glacial acetic acid (20 m~) at 100C
for 6 hours. After cooling, the product was collected, washed and dried to yield 31.0g o~ the desired compound, m.p. 204-206C.
S~nthe is C3 4_methyl- ~ ~henoxy cinnamic acid was prepared by reacting 4_methyl benzaldehyde (120g., 1 mol) with phenoxyacetic acid (167g., 1.1 mol) in a mixture of acetic anhydride (250 m~
2~5 mol) and trieth~lamine (101 mQ 1 mol) at 140C for 5 hours. The cooled deep red solution was poured into 5 litres of a mixture of 1 volum~.of concentrated hydrochloric :
acid and 4 volumes of water and the resultant oil separated, washed with water and then with a 20% (w/v) solution of potassium bisulphite (1 litre) to yield the crude product : which was collected, washed and recrystalli~ed from aqueous ~ ethanol to give 22g of the desired compound m.p 188_190C.
i, Synthesis C4 4-az~do_~ cyano cinnamic acid.~was prepared according to the method describçd in Example 3 of British Specification r~ ? ~ ~o~ o~
No.1,377,747. m.p lG0-lG~ dec.
Synthesis C5 Eth~l h~o~en cinnamylidene malonate was prepared by reacting cinnamaldehyde (31.6 mQ0.2633 mol.) with ethyl _14-744~
potassium malona-te (35.7g 0.26 mol) in glacial acetic acid (5.5 m~ ) at 100C for six hours. After cooling~ the product was collected, washed with a little cold acetic acid and then dissolved in water, extracted with ether and the aqueous layer acidified with dilutchydrochloric acid to yield 25.3 g of the desired product.
Synthesis C6 ~ _(2-furyl) acrylic acid was prepared according to the method described in Organic Syntheses, Collective Vol. III Page ; 425, 1955, m.p. 140-141C.
Synthesis C7 a-cyano-~-methylcinnamvlideneacetic acid was prepared by reacting benzyli-lene acetone (49g 0.33mol.) with ethyl cyanoacetate (38g. 0.33 mol) using, as catalyst, a mixture of ammonium acetate (5g) and acetic acid (15g) in benzene (250 m ~ he reaction mixture was refluxed and the water of reaction removed by azeotropic ~1istillation for a period of i five hours. ~he cooled solution was washed with water, dried over magne~ium sulphate and -the solvent evaporated off to yield a yellow crystalline mass.
A solution of potassium hydroxide (7~0g) in methanol (350 m~)was added and the ~ixture refluxed for 6 hour~
cooled, poured into 30/~ hydrochloric acid (400 mQ) and the precipitate collected and recrys-tallised from aqueous ethanol to yield 12.34g of the desired product m~p. 116 _ 118C.
EX~MP~E 1 (i) Prep_aration of a photosensitive 2 alkali soluble resin 5g (0.032 mol) of the polymer prepared in synthesis Al was dissolved in 2-~utanone (100 mR) admixed with cinnamylidene ~ 7~1~4 ':
malonic acid (synthesis B2) (9.17g 0.042 mol) and benzyltri-ethylammonium chloride (0.4g). The mixture was heated at 80C for fi~e hours and then cooled and precipitated into water (2 l). The resultant pale yellow light sensitive polymer was filtered off and driad at 40C in air to yield 10:4g.
The acid equivalent was 492.
(ii) PreParation of a printin~r plate 2g of the light-sensitive polymer was dissolved in 2_butanone (lO0 mR) coated, by means of a horizontal whirler, on to a ., .
sheet of grained and anodised alumiinium and dried by heating at 80C for 2 minutes. Exposure of the resultant light sensitive plate to a 4000 watt pulsed xenon lamp through a negative for 2 minutes followed by immersion in a 5.~/o aqueou~
solution of sodium metasilicate resulted in a printing plate from which many satisfactory copies could be taken.
~i) Preparation of a photosensitive, alkali soluble resin_ 5~ (0.032 mol) of the polymer prepared in Synthesis Al was dissolved in 2_butanone (lO0 m~) and treated with 3_nitrocinnamylidenem~lonic acid (Synthesis Bl) (10.78g 0.41 mol) and benzyltriethylammoni~m chloride (0.4g) and the mixture heated at 80C for four hours. Cinnamylidene-a -cyanoacetic acid (Synthesis Cl) (25.47g 0.128 mol) and benzyltriethylammonium chloride (0.4g) were then added and heating conti~ued a further two hours. The cooled reaction mixture was diluted with an equal volume of 2~butanone, filtered and the filtrates poured into l~ trichloroethane (lL) whereupon a polymer separated as a flocculent yellow precipitate which was collected on a filter, sucked dry
7~44 and redissolved in acetone (100 m~). This solution was poured into a mixture of water(2~) and concentrated hydrochloric acid (150 m~) and the precipitated resin collectedij washed an~ dried to yield 9.63~. of the desired product having ~max 317 nm and acid equivalent 446.3.
(ii) Preprearation of a ~rinting ~late ; 3g of the above photosensitive resin and 0.3g of 2,6-dianisyl-4_ phenylthiapyrilium perchlorate were dissolved in 2-butanone (100 mQ), filtered and applied by means of a horizontal whirler to the surface of a sheet of electro grained and anodised aluminium to give a coating weight of lg per i~ square metre. After drying at 80 C for two minutes, the ~; resultant light sensitive plate was exposed for 40 seconds in a printing down frame in contact with a negative to a 4000 watt pulsed xenon lamp at a distance of 0.65 metres.
The exposed plate was developed by swabbing with a 5.7.
aqueous solution of so~i~m metasilicate, rinsed with water inked with a ~;reasy ink.
EXAMP~E 3 (i) Prep~ation of a phososensitive, alkali soluble resin Using the proceduré set forth in Example 2 (i) 5 g (0.032 mol)-of poly (2,3-epoxypropylmethacrylate) Synthesis Al) were reacted with cinnamylidene malonic acid (Synthesis B2), ; (8 9g , 0.041 mol) for two hours and then with 4_ chloro-a-phenyl cinnamic acid (Synthesis C2) ~16.5g 0.064 mol) for a further four hours to yield 10.5g Ol the required product having ~max 319n.m and an acid equivalent of 490.4.
'~
' `~ 7444 (ii) Preparation of a printing plate (a) " .
3g of the above photosensitive resin and 0~3g. of 1,2-benzanthraquinone were dissolved in 2-butanone (100 ml) filtered and applied by means of a whirler to the surface of a sheet of electrograined and anodised aluminium to give a coating weight of lg, per square metre, After drying, the resultant light sensitive plate was exposed for 40 secs through a Stouffer stepwedge and developed in the manner described in Example 2 (ii), There was obtained a printing plate with six steps of the step-wedge fully hardened and inked up.
~iii) Preparation of a printing plate (b) ~xample 3(ii) was repeated except that crystal ~iolet dye (0,06g) was additionally included in the coating solution~
The presence of a dye in the exposed light sensitive coating was shown to facilitate removal of the unhardened alkali soluble areas by providing a clearly defined, visible image which increased in contrast as the development proceeded, ~EXAMPLE 4 (i) Preparation_of a photosensitive, alkali soluble resin Using the procedure set forth in Example 2(i) 5g (0,032 mol) of poly (2,3-epoxypropyl methacrylate) (Synthesis Al) was reacted with 2-nitrocinnamylidene malonic acid (Synthesis B3) (10,78g,, 0,41 mol,) for two hours and then with 4-methyl-~-phenoxy cinnamic acid (Synthesis C3) (16.25g 0,064 mol) for a further four hours to yield 8g, of the required product having ~max. 330n,m~, an acid equivalent of 485.2 and containing 2,~% N.
(ii) Preparation of a printing plate 3g, of the above photosensitive resin and 0,3g eosin bm~
'` 11al7~4 were dissolved in 2-butanone (100 mQ) filtered and applied to a sheet of electrograined and anodised aluminium to form a light sensitive plate which was exposed for 2 minutes and processed as in Example 2 (ii), A high quality printing plate ., :
was obtained, ;; EXAMPLE 5 (i) Preparation of a photosensitive, alkali soluble .., resin Using the procedure set forth in Example 2~i), 5g ~0,032 mol) of poly(2,3-epoxypropylmethacrylate), (Synthesis Al) i were reacted with ~-chlorocinnamylidene malonic acid (Synthesis B4), ~10.35g 0.041 mol.) for three hours and then with 4-azido-~-cyanocinnamic acid ~Synthesis C4) (17.55g, 0,082 mol) for a ; further three hours to yield 8,4g of the desired mixed ester resin having ~ max~ 327n,m., an acid equivalent of 558.5 and containing 1.95%N, (ii) Preparation of a printing plate 3g of the above photosensitive resin and 0.03g eosin were dissolved in 2-butanone ~100 mQ)~ and applied to a sheet of electrograined aluminium to form a light sensitive plate which was exposed for 2 minutes and processed as in Example 2 A high quality printing plate was obtained, (i) Preparation of a photosensitive, alkali soluble resin - .. , ... , , .. w Using the procedure set forth in Example 2(i), 5g ~0,032 mol) of poly~2,3-epoxy propyl methacrylate) ~Synthesis Al) were reacted with 4-nitro-~-chlorocinnamylidene malonic acid (Synthesis B5), (12~2g 0~041 mol) for five hours, and then with ethyl hydrogen cinnamylidene malonate (Synthesis C5) (9.68g, 30 ~ 039 mol.) for a further hour to yield 10.025 g. of the desired mixed ester ~ bm~
,. .
g7444 :
resin having~ max 347 nm and an acid equivalent of 493.4 and containing 2.0%N.
(ii) Preparation of a printin~_~late 3g of the above photosensitive resin and 0.3g of eosin were dissolved in 2-butanone (100 ml), filtered and applied to a sheet of electrograined and anodised aluminium to form a light sensitive plate which was exposed and processed according to the procedure described in Example 2(ii) h high quality printing plate was obtained.
EX~MP~E 7 (i~ Preparation of a photosensitive, alkali soluble resin Using the procedure set forth in Example 2 (i), 5g (0.032 mol) or poly(2,3-epoxypropyl methacrylate)(Synthesis Al) were reacted with cinnamylidene malonic acid (Synthesis B2) (8.94g., 0 041 mol) for two hours and then with acrylic acid (9.16g 0.126 mol.) for a further four hours to yield 12.15g of the desired mixed ester resin, having an acid equivalent of 501Ø
(ii) Preparation of a ~printing plate 3g of the above photosensiti~e resin and 0.3g eosin were~
dissolved in 2_butanone (100 m~) and the fLltered solution was applied to a sheet ol electrograined and anodised aluminium.
The resultant light sensitive plate was exposed for one minute and processed as in Example 2 (ii) to give a hi~h quality printing plate.
(i) Preparation of a photosensitive, alkali soluble resin .
Using the procedure set forth in Ex~mple 2(i), 5g (.029 mol.
epoxide) of poly_(2,3_epoxy~rop~ethacrylate_co_styrene) .
.
., .
(Synthesis A4) were reacted with cinnamylidene malonic acid (S~,~nthesis B2j (8.28g, 0.038 mol) for two hours and then with ~-(2-furyl) acrylic acid (Synthesis C6) (17,4g, 0.176 mol) for a further four hours to yield 10.6g of the desired mixed ester resin having an acid equivalent of 469.8.
(ii) Preparation of a printin~ plate 3g of the above photosensitive resin and 0.3g eosin were dissolved in 2-butanone (100 mQ) The solution was filtered and applied by means of a whirler to a sheet of electrograined and anodised aluminium to form a light sensitive plate which was exposed for one minute and processed as in Example 2 (ii) to give a high quality printing plate.
~XAMPLE 9 (i) Preparation o~ a photosensitive, alkali soluble resin Using the procedure set forth in Example 2 (i) 5 g (0.034 mol, epoxide) of poly(2,3_epoxypropylacrylate_co_ acrylonitrile) (Synthesis ~5) were reacted with cinnamylidene malonic acid (Synthesis B2) (8.28g 0.038 mol) for four hours and then with a-cyano-~_methylcinnamylidene acetic acid (Synthesis C7) (16.19g, 0.076 mol~ for a further two hours to yield 9.8g of the desired mixed es-ter resin having ~ max 321 n.m + an acid equivalent of 53101.
(ii) Preparation of a printin~ plate i .
' ~g of the above photosensitive resin and O.~g 1,2_ ' benzanthraquinone were dissolved in 2_butanone (lOC m~), The solution was filtered and applied by means of a whirler to a sheet of electrograined and anodised aluminium and dried to form a light sensitive plate which was exposed as ,' described in Example 2(ii). The exposed plate was then cut .
.
-21_ , ' ': ' .. ~ ' ' :~
- . ~
~ 7~44 :
into three equal parts. 1 part was treated with 5. 7% aqueous sodium metasilicate soluti,on, rinsed and inXed up. 1 part was treated with ?,5% aqueous sodium hydroxide solution, rinsed and inked up. 1 part was treated with 0.033 molar trisodium phosphate solutlon rir~sed and inked up- All three had similar printing capabilities.
EVl~MPLE 10 (i) Preparation of a photosensitive, alkali soluble resin 5g, ( . 02~ mol) poly (2,3-epoxypropyl methacrylate -co-dodecyl methacrylate) (Synthesis A3) were reacted with cinnamyli_ dene malonic acid (Synthesis B2) (13.74g 0.063 mol) for 6 hours at 80C using triethylamine (0.125 m ~) as catalyst for the ", esterification. The homoester resin was isolated by the procedure described in ~xample l(i) to yield ~.8g of the product~ having an acid equivalent of 461.6, -`' (ii) Pre~aration of a printing plate 3g of the above photosensi-tive resin and 0.3g of eosin ~' were dissolved in 2_butanone (100 m Q). The solution was filtered and applied to a sheet of electrograined and anodised , aluminium to form a light sensitive plate which was exposed for one minute, developed using a 5,7% aqueous sodium ,~ metasilicate solution and rinsed with water. This resul~d in a hydrophobic, ink receptive image area due to the incorporation of dodecyl methacrylate units in the substrate polymer chain.
~he printing plate had excellent printing characteristics.
(i) Preparation of a ~ _ ~ " ~
, Usin~ the procedure set forth in Example 2 (i) 5 g.
(0.032 mol ) of po~y(2,3-epoxypropyl methacr~late) ~ynthesis ~1) ' , -22_ ..
. .
'' ' ~ ' . .
~ 7~4 were reacted with cinnamylidene malonic acid (S~nthesis B2) (8.94g, 0.04~ mol.) for two hours and then with octanoic acid (18.14g, 0.126 mol) for four hours to yield 10.8g of the desired ~ixed ester reæin having an acid equivalent - of 613.6.
(ii) ~reparation of a ~rintin~ plate ., I
¦ A printing plate was prepared in accordance with the f procedure described in Example (ii) and was showni to `;1 have similar characteristics due to the incorporation of octanoate ester groups in the photosensitive resin.
(i) Preparation of a photosensitivel alkali soluble resin i 5g (0.032 mol.) poly (2,3_epoxypropylmethacrylate) (Synthesi~
Al) and benzyl triethylammonium bromi~e (0 2g) were di solved in 2-butanone (100 ml), treated with propionyl chloride (0.29g 0.0032 mol) and heated to 80C for one hour. Cinnamylidene malonic acid (~3.74 g 0.063 mol) and benzyltriethylammonium bromide (0.4g) were then added and heating continued for a further 5 hours, whereupon the product was isolated by the procedure described in Example 2 (i) to yield 9.1g of the desired mixed ester resin ha~ing an acid equivalent of 422.9, and a chlorine content of 1.97. (w/w).
~; (ii) Preparation of a_ ~ e ; A printing plate was prepared in accordance with the . .
procedure described in Example 10 (ii). It gave many satisfactor~ copies without showint; signs of wear.
EXAMP~E 13 (i) Preparation of~ photosensitive~ alkall soluble resin ~~ Using the procedure set forth in Example 2(i) 5g (0.038 mol epoxide) poly-(2,3_epoxypropyl acrylate) .
~ 3 , ~ ~
.
., . ~
~Synthesis A2) were reacted with cinnamylidene malonic acid (Synthesis B2) (17.0g, 0.075 mol.) for 2~ hours and then with acetic acid (8.9cm3, 9.388g., 0.156 mol,) for a further 3~
hours to yield 10.5g of the desired mixed ester resin having an acid equivalent of 443.1.
(ii) Preparation of a printing plate (a) A printing plate was prepared in accordance with the procedure described in Example 4(ii). It was capable of producing many high quality prints without sign of lma~e wear.
(iii~ Preparation of a printin~ plate (b) A piece of the light sensitive plate prepared as above was exposed for fifteen minutes to a 250 watt tungsten light bulb at a distance of 0.5m. and then developed and inked as described in Example 2(ii) to give a high quality printing plate.
(iv) Preparation of a printing plate (c).
A further piece of the above prepared, light sensitive plate was exposed to an argon ion laser operating in the ultraviolet to given an expc~re of 50 millijoules per square cm.
and resulted in a high quality printing plate.
EXA~LE 14 .~ . .
(~ Preparation of a photosensitive, alkali soluble resin .~.
; ~sing the procedure d~scribed in Example 2(i) 15g (0.096 mol) of poly (2,3-epoxypropyl methacrylate) Synthesis Al) were reacted with cinnamylidene malonic acid (Synthesis B2) (26.8g 0.123 mol) for four hours and then with trichloroacetic acid (30g, 0.18 mol,) for a further two hours to yield 31g of the desired mixed ester having an acid equivalent of 544.1 .
_24_ : .
:
.:
- . ~ ~' . .' ~
~7~4 (ii) PreParatiOn of a printing plate A printing plate was prepared in accordance with the procedure described in Example 4(ii).It was capable of :.
~ producing high quality copies.
; EXAMPLE 15 (i) Preparation of a ~hotosensitive? alkali soluble resin , lOg. of the product from Example 14 were di ~olved ~d , in 2-butanone (100 ml) ~reated with acetic anhydride (0.23g, '' 0.00225 mol) for 4 hours, yielding 9.8g. of acetylated product.
(ii) ~reparation of a printing plate , ' A printingplate was prepared in accordance with the ! procedure described in Example 4(ii). It had an extremely j hydrophobic i,mage area7 and was capable of producin~ man~
': j `"'! copies without showing any sign of wear.
'.:"' 1 -; ~
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(ii) Preprearation of a ~rinting ~late ; 3g of the above photosensitive resin and 0.3g of 2,6-dianisyl-4_ phenylthiapyrilium perchlorate were dissolved in 2-butanone (100 mQ), filtered and applied by means of a horizontal whirler to the surface of a sheet of electro grained and anodised aluminium to give a coating weight of lg per i~ square metre. After drying at 80 C for two minutes, the ~; resultant light sensitive plate was exposed for 40 seconds in a printing down frame in contact with a negative to a 4000 watt pulsed xenon lamp at a distance of 0.65 metres.
The exposed plate was developed by swabbing with a 5.7.
aqueous solution of so~i~m metasilicate, rinsed with water inked with a ~;reasy ink.
EXAMP~E 3 (i) Prep~ation of a phososensitive, alkali soluble resin Using the proceduré set forth in Example 2 (i) 5 g (0.032 mol)-of poly (2,3-epoxypropylmethacrylate) Synthesis Al) were reacted with cinnamylidene malonic acid (Synthesis B2), ; (8 9g , 0.041 mol) for two hours and then with 4_ chloro-a-phenyl cinnamic acid (Synthesis C2) ~16.5g 0.064 mol) for a further four hours to yield 10.5g Ol the required product having ~max 319n.m and an acid equivalent of 490.4.
'~
' `~ 7444 (ii) Preparation of a printing plate (a) " .
3g of the above photosensitive resin and 0~3g. of 1,2-benzanthraquinone were dissolved in 2-butanone (100 ml) filtered and applied by means of a whirler to the surface of a sheet of electrograined and anodised aluminium to give a coating weight of lg, per square metre, After drying, the resultant light sensitive plate was exposed for 40 secs through a Stouffer stepwedge and developed in the manner described in Example 2 (ii), There was obtained a printing plate with six steps of the step-wedge fully hardened and inked up.
~iii) Preparation of a printing plate (b) ~xample 3(ii) was repeated except that crystal ~iolet dye (0,06g) was additionally included in the coating solution~
The presence of a dye in the exposed light sensitive coating was shown to facilitate removal of the unhardened alkali soluble areas by providing a clearly defined, visible image which increased in contrast as the development proceeded, ~EXAMPLE 4 (i) Preparation_of a photosensitive, alkali soluble resin Using the procedure set forth in Example 2(i) 5g (0,032 mol) of poly (2,3-epoxypropyl methacrylate) (Synthesis Al) was reacted with 2-nitrocinnamylidene malonic acid (Synthesis B3) (10,78g,, 0,41 mol,) for two hours and then with 4-methyl-~-phenoxy cinnamic acid (Synthesis C3) (16.25g 0,064 mol) for a further four hours to yield 8g, of the required product having ~max. 330n,m~, an acid equivalent of 485.2 and containing 2,~% N.
(ii) Preparation of a printing plate 3g, of the above photosensitive resin and 0,3g eosin bm~
'` 11al7~4 were dissolved in 2-butanone (100 mQ) filtered and applied to a sheet of electrograined and anodised aluminium to form a light sensitive plate which was exposed for 2 minutes and processed as in Example 2 (ii), A high quality printing plate ., :
was obtained, ;; EXAMPLE 5 (i) Preparation of a photosensitive, alkali soluble .., resin Using the procedure set forth in Example 2~i), 5g ~0,032 mol) of poly(2,3-epoxypropylmethacrylate), (Synthesis Al) i were reacted with ~-chlorocinnamylidene malonic acid (Synthesis B4), ~10.35g 0.041 mol.) for three hours and then with 4-azido-~-cyanocinnamic acid ~Synthesis C4) (17.55g, 0,082 mol) for a ; further three hours to yield 8,4g of the desired mixed ester resin having ~ max~ 327n,m., an acid equivalent of 558.5 and containing 1.95%N, (ii) Preparation of a printing plate 3g of the above photosensitive resin and 0.03g eosin were dissolved in 2-butanone ~100 mQ)~ and applied to a sheet of electrograined aluminium to form a light sensitive plate which was exposed for 2 minutes and processed as in Example 2 A high quality printing plate was obtained, (i) Preparation of a photosensitive, alkali soluble resin - .. , ... , , .. w Using the procedure set forth in Example 2(i), 5g ~0,032 mol) of poly~2,3-epoxy propyl methacrylate) ~Synthesis Al) were reacted with 4-nitro-~-chlorocinnamylidene malonic acid (Synthesis B5), (12~2g 0~041 mol) for five hours, and then with ethyl hydrogen cinnamylidene malonate (Synthesis C5) (9.68g, 30 ~ 039 mol.) for a further hour to yield 10.025 g. of the desired mixed ester ~ bm~
,. .
g7444 :
resin having~ max 347 nm and an acid equivalent of 493.4 and containing 2.0%N.
(ii) Preparation of a printin~_~late 3g of the above photosensitive resin and 0.3g of eosin were dissolved in 2-butanone (100 ml), filtered and applied to a sheet of electrograined and anodised aluminium to form a light sensitive plate which was exposed and processed according to the procedure described in Example 2(ii) h high quality printing plate was obtained.
EX~MP~E 7 (i~ Preparation of a photosensitive, alkali soluble resin Using the procedure set forth in Example 2 (i), 5g (0.032 mol) or poly(2,3-epoxypropyl methacrylate)(Synthesis Al) were reacted with cinnamylidene malonic acid (Synthesis B2) (8.94g., 0 041 mol) for two hours and then with acrylic acid (9.16g 0.126 mol.) for a further four hours to yield 12.15g of the desired mixed ester resin, having an acid equivalent of 501Ø
(ii) Preparation of a ~printing plate 3g of the above photosensiti~e resin and 0.3g eosin were~
dissolved in 2_butanone (100 m~) and the fLltered solution was applied to a sheet ol electrograined and anodised aluminium.
The resultant light sensitive plate was exposed for one minute and processed as in Example 2 (ii) to give a hi~h quality printing plate.
(i) Preparation of a photosensitive, alkali soluble resin .
Using the procedure set forth in Ex~mple 2(i), 5g (.029 mol.
epoxide) of poly_(2,3_epoxy~rop~ethacrylate_co_styrene) .
.
., .
(Synthesis A4) were reacted with cinnamylidene malonic acid (S~,~nthesis B2j (8.28g, 0.038 mol) for two hours and then with ~-(2-furyl) acrylic acid (Synthesis C6) (17,4g, 0.176 mol) for a further four hours to yield 10.6g of the desired mixed ester resin having an acid equivalent of 469.8.
(ii) Preparation of a printin~ plate 3g of the above photosensitive resin and 0.3g eosin were dissolved in 2-butanone (100 mQ) The solution was filtered and applied by means of a whirler to a sheet of electrograined and anodised aluminium to form a light sensitive plate which was exposed for one minute and processed as in Example 2 (ii) to give a high quality printing plate.
~XAMPLE 9 (i) Preparation o~ a photosensitive, alkali soluble resin Using the procedure set forth in Example 2 (i) 5 g (0.034 mol, epoxide) of poly(2,3_epoxypropylacrylate_co_ acrylonitrile) (Synthesis ~5) were reacted with cinnamylidene malonic acid (Synthesis B2) (8.28g 0.038 mol) for four hours and then with a-cyano-~_methylcinnamylidene acetic acid (Synthesis C7) (16.19g, 0.076 mol~ for a further two hours to yield 9.8g of the desired mixed es-ter resin having ~ max 321 n.m + an acid equivalent of 53101.
(ii) Preparation of a printin~ plate i .
' ~g of the above photosensitive resin and O.~g 1,2_ ' benzanthraquinone were dissolved in 2_butanone (lOC m~), The solution was filtered and applied by means of a whirler to a sheet of electrograined and anodised aluminium and dried to form a light sensitive plate which was exposed as ,' described in Example 2(ii). The exposed plate was then cut .
.
-21_ , ' ': ' .. ~ ' ' :~
- . ~
~ 7~44 :
into three equal parts. 1 part was treated with 5. 7% aqueous sodium metasilicate soluti,on, rinsed and inXed up. 1 part was treated with ?,5% aqueous sodium hydroxide solution, rinsed and inked up. 1 part was treated with 0.033 molar trisodium phosphate solutlon rir~sed and inked up- All three had similar printing capabilities.
EVl~MPLE 10 (i) Preparation of a photosensitive, alkali soluble resin 5g, ( . 02~ mol) poly (2,3-epoxypropyl methacrylate -co-dodecyl methacrylate) (Synthesis A3) were reacted with cinnamyli_ dene malonic acid (Synthesis B2) (13.74g 0.063 mol) for 6 hours at 80C using triethylamine (0.125 m ~) as catalyst for the ", esterification. The homoester resin was isolated by the procedure described in ~xample l(i) to yield ~.8g of the product~ having an acid equivalent of 461.6, -`' (ii) Pre~aration of a printing plate 3g of the above photosensi-tive resin and 0.3g of eosin ~' were dissolved in 2_butanone (100 m Q). The solution was filtered and applied to a sheet of electrograined and anodised , aluminium to form a light sensitive plate which was exposed for one minute, developed using a 5,7% aqueous sodium ,~ metasilicate solution and rinsed with water. This resul~d in a hydrophobic, ink receptive image area due to the incorporation of dodecyl methacrylate units in the substrate polymer chain.
~he printing plate had excellent printing characteristics.
(i) Preparation of a ~ _ ~ " ~
, Usin~ the procedure set forth in Example 2 (i) 5 g.
(0.032 mol ) of po~y(2,3-epoxypropyl methacr~late) ~ynthesis ~1) ' , -22_ ..
. .
'' ' ~ ' . .
~ 7~4 were reacted with cinnamylidene malonic acid (S~nthesis B2) (8.94g, 0.04~ mol.) for two hours and then with octanoic acid (18.14g, 0.126 mol) for four hours to yield 10.8g of the desired ~ixed ester reæin having an acid equivalent - of 613.6.
(ii) ~reparation of a ~rintin~ plate ., I
¦ A printing plate was prepared in accordance with the f procedure described in Example (ii) and was showni to `;1 have similar characteristics due to the incorporation of octanoate ester groups in the photosensitive resin.
(i) Preparation of a photosensitivel alkali soluble resin i 5g (0.032 mol.) poly (2,3_epoxypropylmethacrylate) (Synthesi~
Al) and benzyl triethylammonium bromi~e (0 2g) were di solved in 2-butanone (100 ml), treated with propionyl chloride (0.29g 0.0032 mol) and heated to 80C for one hour. Cinnamylidene malonic acid (~3.74 g 0.063 mol) and benzyltriethylammonium bromide (0.4g) were then added and heating continued for a further 5 hours, whereupon the product was isolated by the procedure described in Example 2 (i) to yield 9.1g of the desired mixed ester resin ha~ing an acid equivalent of 422.9, and a chlorine content of 1.97. (w/w).
~; (ii) Preparation of a_ ~ e ; A printing plate was prepared in accordance with the . .
procedure described in Example 10 (ii). It gave many satisfactor~ copies without showint; signs of wear.
EXAMP~E 13 (i) Preparation of~ photosensitive~ alkall soluble resin ~~ Using the procedure set forth in Example 2(i) 5g (0.038 mol epoxide) poly-(2,3_epoxypropyl acrylate) .
~ 3 , ~ ~
.
., . ~
~Synthesis A2) were reacted with cinnamylidene malonic acid (Synthesis B2) (17.0g, 0.075 mol.) for 2~ hours and then with acetic acid (8.9cm3, 9.388g., 0.156 mol,) for a further 3~
hours to yield 10.5g of the desired mixed ester resin having an acid equivalent of 443.1.
(ii) Preparation of a printing plate (a) A printing plate was prepared in accordance with the procedure described in Example 4(ii). It was capable of producing many high quality prints without sign of lma~e wear.
(iii~ Preparation of a printin~ plate (b) A piece of the light sensitive plate prepared as above was exposed for fifteen minutes to a 250 watt tungsten light bulb at a distance of 0.5m. and then developed and inked as described in Example 2(ii) to give a high quality printing plate.
(iv) Preparation of a printing plate (c).
A further piece of the above prepared, light sensitive plate was exposed to an argon ion laser operating in the ultraviolet to given an expc~re of 50 millijoules per square cm.
and resulted in a high quality printing plate.
EXA~LE 14 .~ . .
(~ Preparation of a photosensitive, alkali soluble resin .~.
; ~sing the procedure d~scribed in Example 2(i) 15g (0.096 mol) of poly (2,3-epoxypropyl methacrylate) Synthesis Al) were reacted with cinnamylidene malonic acid (Synthesis B2) (26.8g 0.123 mol) for four hours and then with trichloroacetic acid (30g, 0.18 mol,) for a further two hours to yield 31g of the desired mixed ester having an acid equivalent of 544.1 .
_24_ : .
:
.:
- . ~ ~' . .' ~
~7~4 (ii) PreParatiOn of a printing plate A printing plate was prepared in accordance with the procedure described in Example 4(ii).It was capable of :.
~ producing high quality copies.
; EXAMPLE 15 (i) Preparation of a ~hotosensitive? alkali soluble resin , lOg. of the product from Example 14 were di ~olved ~d , in 2-butanone (100 ml) ~reated with acetic anhydride (0.23g, '' 0.00225 mol) for 4 hours, yielding 9.8g. of acetylated product.
(ii) ~reparation of a printing plate , ' A printingplate was prepared in accordance with the ! procedure described in Example 4(ii). It had an extremely j hydrophobic i,mage area7 and was capable of producin~ man~
': j `"'! copies without showing any sign of wear.
'.:"' 1 -; ~
;, A ~ .
..,,j '.' ..,.,1 "
.~"j , , . .
i , .
,, .
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, .:. , ` :
Claims (10)
- We Claim: -l. photopolymerisable material which comprises a polymer including a plurality of structural units represented by the Formula (I):
in which Rl represents a hydrogen atom or a methyl group;
R2 represents a hydrogen atom, an alkyl or substituted alkyl group, an aryl or substituted aryl group, or a heterocyclic or substituted heterocyclic group; R3, R4 and R5, which may be the same or different, each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an aralkyl group, an aralkoxy group or an alkoxy carbonyl group; Z represents a hydroxyl group, or an ester group and a is an integer greater than or equal to 1 - 2. A photopolymerisable material as claimed in Claim 1, wherein in Formula I, (i) R2 represents phenyl and R3, R4 and R5 represent hydrogen;
(ii) R2 represents 2-nitrophenyl and R3, R4 and R5 represent hydrogen;
(iii) R2 represents 3-nitrophenyl and R3, R4 and R5 represent hydrogen;
(iv) R2 represents phenyl, R3 represents chloro and R4 and R5 represent hydrogen; or (v) R2 represents 4-nitrophenyl, R3 represents chloro and R4 and R5 represent hydrogen. - 3. A photopolymerisable material as claimed in Claim 1 wherein the polymer additionally includes a plurality of structural units having the Formula (II);
in which zl represents a hydroxyl group, an ester group or a halogen atom, Rl to R5 represent the same as in Formula I, R6 represents the same as R3 to R5 in Formula I and b is O or an integer greater than or equal to 1. - 4. A photopolymerisable material as claimed in Claim 3, wherein in Formula II, (i) b is 0, and R2, R5 and R6 all represent hydrogen;
(ii) b is 0, R2 and R5 represent hydrogen, and R6 represents methyl;
(iii) b is o, x2 represents phenyl and R5 and R6 represent hydrogen;
(iv) b is 0, R2 represents 4-methoxyphenyl, R5 represents hydrogen and R6 represents cyano;
(v) b is 0, R2 represents 4-chloro-phenyl, R5 represents hydrogen and R6 represents phenyl;
(vi) b is 0, R2 represents 4-methyl phenyl, R5 is hydrogen and R6 is phenoxy;
(vii) b is 0, R2 represents 4-azido phenyl, R5 represents hydrogen and R6 represents cyano;
(iix) b is 0, R2 represents 2-furyl, and R5 and R6 represent hydrogen;
(ix) b is 1, R2 represents phenyl, R3, R4 and R5 represent hydrogen and R6 is cyano;
(x) b is 1, R2 is phenyl, R3, R4 and R5 represent hydrogen and R6 represents ethoxy carbonyl, or (xi) b is 1, R2 represents phenyl, R3 and R4 represent hydrogen, R5 represents methyl and R6 represents cyano. - 5. A photopolymerisable material as claimed in Claim 1, wherein the polymer additionally includes a plurality of structural units having the Formula (III);
in which Rl and zl represent the same as in Formula II and R7 represents an alkyl or substituted alkyl group, an aryl or substituted aryl group, or a heterocyclic or substituted heterocyclic group. - 6. A photopolymerisable material as claimed in Claim 5, wherein in Formula III, (i) R7 represents methyl and Z1 represent hydroxyl;
(ii) R7 represents heptyl and Z1 represents hydroxyl;
(iii) R7 represents ethyl and Z1 represents chlorine; or (iv) R7 represents trichloromethyl and Z1 represents hydroxyl. - 7. A photopolymerisable material as claimed in Claim 1, wherein the polymer additionally includes a plurality of structural units derived from an unsaturated addition polymerisable monomer.
- 8. A photopolymerisable material as claimed in Claim 7, wherein said polymerisable monomer is dodecyl methacrylate, styrene or acrylonitrile.
- 9. A light sensitive plate comprising a photopolymerisable material according to Claim 1 coated on a substrate.
- 10. A method of producing a printing plate which method comprises image-wise exposing a light sensitive plate as claimed in Claim 9 and then removing non-light struck areas of the material from the substrate using an aqueous alkaline solution of at least one inorganic salt.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB52522/75A GB1572441A (en) | 1975-12-23 | 1975-12-23 | Photopolymerisable polymers with free carboxyl groups and printing plates therefrom |
| GB52522/75 | 1975-12-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1107444A true CA1107444A (en) | 1981-08-18 |
Family
ID=10464243
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA268,315A Expired CA1107444A (en) | 1975-12-23 | 1976-12-21 | Light-sensitive materials |
Country Status (27)
| Country | Link |
|---|---|
| US (1) | US4263394A (en) |
| JP (1) | JPS5286488A (en) |
| AT (1) | AT348552B (en) |
| AU (1) | AU510145B2 (en) |
| BE (1) | BE849803A (en) |
| BR (1) | BR7608579A (en) |
| CA (1) | CA1107444A (en) |
| CH (1) | CH629314A5 (en) |
| CS (1) | CS212783B2 (en) |
| DE (1) | DE2658272A1 (en) |
| DK (1) | DK579976A (en) |
| ES (1) | ES454521A1 (en) |
| FI (1) | FI64863C (en) |
| FR (1) | FR2336707A1 (en) |
| GB (1) | GB1572441A (en) |
| IE (1) | IE44405B1 (en) |
| IT (1) | IT1065419B (en) |
| KE (1) | KE3336A (en) |
| LU (1) | LU76465A1 (en) |
| MW (1) | MW5276A1 (en) |
| NL (1) | NL7614259A (en) |
| NO (1) | NO764338L (en) |
| NZ (1) | NZ182955A (en) |
| PL (1) | PL103094B1 (en) |
| SE (1) | SE424642B (en) |
| ZA (1) | ZA767635B (en) |
| ZM (1) | ZM15276A1 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4343888A (en) | 1980-05-01 | 1982-08-10 | E. I. Du Pont De Nemours And Company | Use of radiation crosslinkable polyesters and polyesterethers in printing plates |
| US4284710A (en) | 1980-05-01 | 1981-08-18 | E. I. Du Pont De Nemours And Company | Radiation crosslinkable polyesters and polyesterethers |
| US4592816A (en) * | 1984-09-26 | 1986-06-03 | Rohm And Haas Company | Electrophoretic deposition process |
| DE3528929A1 (en) * | 1985-08-13 | 1987-02-26 | Hoechst Ag | RADIATION-SENSITIVE MIXTURE, THIS CONTAINING RADIATION-SENSITIVE RECORDING MATERIAL AND METHOD FOR THE PRODUCTION OF RELIEF IMAGES |
| CA2218752A1 (en) * | 1995-04-27 | 1996-10-31 | Minyu Li | Negative-acting no-process printing plates |
| US5910395A (en) * | 1995-04-27 | 1999-06-08 | Minnesota Mining And Manufacturing Company | Negative-acting no-process printing plates |
| US6159658A (en) * | 1996-03-19 | 2000-12-12 | Toray Industries, Inc. | Photosensitive resin composition with polymer having an ionic group and having a polymerizable group in the side chain and printing plate materials |
| CA2406160A1 (en) * | 2000-04-13 | 2001-10-25 | Hsc Research And Development Limited Partnership | Compounds for modulating cell proliferation |
| CA2407755A1 (en) * | 2002-10-11 | 2004-04-11 | The Hospital For Sick Children | Inhibition of vegf secretion |
| WO2005012234A1 (en) * | 2003-07-30 | 2005-02-10 | The Hospital For Sick Children | Compounds for modulating cell proliferation |
| JP2007530455A (en) * | 2004-03-26 | 2007-11-01 | エイチエスシー リサーチ アンド ディベロップメント リミテッド パートナーシップ | Compounds that modulate cell proliferation |
| US8778568B2 (en) * | 2010-12-14 | 2014-07-15 | General Electric Company | Optical data storage media and methods for using the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3799915A (en) * | 1971-08-20 | 1974-03-26 | Western Litho Plate & Supply | Photopolymers |
| US3993684A (en) * | 1971-08-20 | 1976-11-23 | Western Litho Plate & Supply Co. | Monomeric compounds |
| US4065430A (en) * | 1973-02-13 | 1977-12-27 | Fuji Photo Film Co., Ltd. | Functional group containing polymer and method of preparing the same |
-
1975
- 1975-12-23 GB GB52522/75A patent/GB1572441A/en not_active Expired
-
1976
- 1976-12-20 SE SE7614315A patent/SE424642B/en not_active IP Right Cessation
- 1976-12-21 CA CA268,315A patent/CA1107444A/en not_active Expired
- 1976-12-21 PL PL1976194590A patent/PL103094B1/en unknown
- 1976-12-21 BR BR7608579A patent/BR7608579A/en unknown
- 1976-12-22 FI FI763683A patent/FI64863C/en not_active IP Right Cessation
- 1976-12-22 MW MW52/76A patent/MW5276A1/en unknown
- 1976-12-22 NO NO764338A patent/NO764338L/no unknown
- 1976-12-22 IE IE2806/76A patent/IE44405B1/en unknown
- 1976-12-22 CH CH1619976A patent/CH629314A5/en not_active IP Right Cessation
- 1976-12-22 NL NL7614259A patent/NL7614259A/en not_active Application Discontinuation
- 1976-12-22 DK DK579976A patent/DK579976A/en not_active Application Discontinuation
- 1976-12-22 AU AU20818/76A patent/AU510145B2/en not_active Expired
- 1976-12-22 DE DE19762658272 patent/DE2658272A1/en not_active Withdrawn
- 1976-12-22 FR FR7638665A patent/FR2336707A1/en active Granted
- 1976-12-22 NZ NZ182955A patent/NZ182955A/en unknown
- 1976-12-23 ZA ZA767635A patent/ZA767635B/en unknown
- 1976-12-23 JP JP15433576A patent/JPS5286488A/en active Pending
- 1976-12-23 IT IT30822/76A patent/IT1065419B/en active
- 1976-12-23 CS CS768572A patent/CS212783B2/en unknown
- 1976-12-23 AT AT964076A patent/AT348552B/en not_active IP Right Cessation
- 1976-12-23 ES ES454521A patent/ES454521A1/en not_active Expired
- 1976-12-23 LU LU76465A patent/LU76465A1/xx unknown
- 1976-12-23 BE BE173590A patent/BE849803A/en not_active IP Right Cessation
- 1976-12-29 ZM ZM152/76A patent/ZM15276A1/en unknown
-
1979
- 1979-06-18 US US06/049,272 patent/US4263394A/en not_active Expired - Lifetime
-
1983
- 1983-10-05 KE KE3336A patent/KE3336A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FR2336707A1 (en) | 1977-07-22 |
| IE44405B1 (en) | 1981-11-18 |
| BE849803A (en) | 1977-06-23 |
| NL7614259A (en) | 1977-06-27 |
| NO764338L (en) | 1977-06-24 |
| IE44405L (en) | 1977-06-23 |
| IT1065419B (en) | 1985-02-25 |
| ATA964076A (en) | 1978-07-15 |
| FI64863B (en) | 1983-09-30 |
| CS212783B2 (en) | 1982-03-26 |
| JPS5286488A (en) | 1977-07-18 |
| MW5276A1 (en) | 1978-02-08 |
| FI64863C (en) | 1984-01-10 |
| KE3336A (en) | 1983-11-04 |
| ES454521A1 (en) | 1977-12-01 |
| DE2658272A1 (en) | 1977-07-14 |
| FI763683A (en) | 1977-06-24 |
| AU510145B2 (en) | 1980-06-12 |
| FR2336707B1 (en) | 1983-04-29 |
| ZA767635B (en) | 1977-11-30 |
| NZ182955A (en) | 1979-04-26 |
| ZM15276A1 (en) | 1978-03-21 |
| DK579976A (en) | 1977-06-24 |
| CH629314A5 (en) | 1982-04-15 |
| AU2081876A (en) | 1978-06-29 |
| PL103094B1 (en) | 1979-05-31 |
| GB1572441A (en) | 1980-07-30 |
| BR7608579A (en) | 1977-12-27 |
| SE7614315L (en) | 1977-06-24 |
| US4263394A (en) | 1981-04-21 |
| SE424642B (en) | 1982-08-02 |
| LU76465A1 (en) | 1977-06-15 |
| AT348552B (en) | 1979-02-26 |
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